Water-based gel cosmetic compositions without film formers

ABSTRACT

Disclosed are water-based cosmetic compositions comprising a synthetic non-associative thickening polymer, a synthetic associative thickening polymer, an emulsifier, and a liquid fatty substance, wherein the composition has a viscosity of from about 2,000 Pa·s to about 90,000 Pa·s at low shear rate as measured on a TA instrument G2 Rheometer.

TECHNICAL FIELD

The present invention relates to water-based gel cosmetic compositionshaving a viscosity profile that mimics commercially available anhydrousgel eyeliners.

BACKGROUND OF THE INVENTION

Cosmetic compositions in gel form are desirable as gels are easy toapply, afford a more consistent and precise coverage than liquids andare not as drying to the skin as powders. Water-based cosmeticcompositions, in particular face and eyeliner compositions, aredesirable as water based cosmetics can be easier to remove, are lesslikely to clog pores, may afford a less shiny and more natural look andfeel, and are less expensive to process when compared to oil orsolvent-based compositions. While aqueous cosmetic compositions areknown, for example U.S. Pat. No. 6,641,823, these compositions are notgels. Most currently marketed gel eyeliners are anhydrous. They are notideal as they contain hydrocarbon solvents (typically isododecane) andhigh volatile silicone fluids (such as cyclopentasiloxane). Theseanhydrous gels typically suffer from inconsistent wear, smudging and aredifficult to remove. They typically are also less fresh and moreuncomfortable to wear than water-based compositions. Additionally,water-based compositions are typically less costly to produce and offera more sustainable environmental platform.

There remains need for a water-based gel cosmetic composition.

The current invention provides water-based gel cosmetic compositionsthat afford a comparable rheological profile to marketed anhydrous gelformulas. This affords the consumer the convenience of gels (e.g. easycontrol, precise product pick-up) having the desirable properties ofboth marketed anhydrous gel formulas (good glide, spreadability,coverage and intensity) and water-based cosmetics (freshness, ease ofremoval, good wear and comfort).

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a water-based gel cosmetic compositioncomprising at least one synthetic non-associative thickening polymer, atleast one synthetic associative thickening polymer, at least oneemulsifier, and at least one liquid fatty substance, said compositionshaving a viscosity at low shear rate of from about 2,000 to about 90,000Pa·s at low shear rate and from about 0.1 to about 3 Pa·s at high shearrate (Method A).

In an embodiment the ratio of the at least one synthetic non-associativethickening polymer to the at least one synthetic associative thickeningpolymer is greater than 1:1.

In another embodiment, the ratio of the at least one syntheticnon-associative thickening polymer to the at least one syntheticassociative thickening polymer is less than or equal to 1:1.

Another embodiment of the invention relates to method of making up akeratinous substance, in particular the eyes, but applying to the eyelids the above-described composition.

Another embodiment of the invention relates to a method of improving atleast one property selected from freshness, long wear, comfort, gentleapplication, color intensity, ease of removal, water and/oroil-resistance, adhesion, malleability, setting viscosity and transferresistance of a gel eyeliner by incorporating in said eyeliner asynthetic non-associative thickening polymer and a synthetic associativethickening polymer.

The composition optionally may include other components appropriate forits intended use such as emollients, pigments, preservatives,neutralizers, vitamins, fillers, waxes, and the like.

DETAILED DESCRIPTION OF THE INVENTION

In the following description of the invention and the claims appendedhereto, it is to be understood that the terms used have their ordinaryand accustomed meanings in the art, unless otherwise specified. Allconcentrations are by weight percent on an active basis unless otherwiseindicated.

“Aqueous phase” means the phase comprising water as well as suchsubstances of a formulation which, due to their hydrophilic character,can be mixed in and/or dissolved in and/or dispersed in water. Theaqueous phase of the composition according to the invention isadvantageously a continuous aqueous phase. A “continuous aqueous phase”means that the composition has a conductivity, measured at 25° C., ofgreater than 23 microSiemens/cm, the conductivity being measured, forexample, using an MPC227 conductimeter from Mettler Toledo and an Inlab730 conductivity measuring cell.

“Associative thickening polymers” or “associative thickeners” arewater-soluble or hydrophobic soluble polymers having low to moderatemolecular weights (up to about 10⁵ g/mol, herein most typically fromabout 10,000 g/mol to about 50,000 g/mol) and containing terminal orpendant hydrophobic ends to a hydrophilic backbone, the hydrophobic endsbeing capable of non-specific hydrophobic association such as thosesimilar to conventional surfactants, and which by itself only slightlyincreases the viscosity of a composition. Associative thickeningpolymers are known in the art. See, e.g. U.S. Pat. No. 6,150,445;WO2011/076792; G. Fonnum et al, “Associative Thickeners:Part I:Synthesis, rheology and aggregation behavior”, Colloid Polymer Sci.271:380-389 (1993); Paint & Coating Testing Manual, 14^(th) Edition (J VKoleske Ed., 1995), pp. 268-288. A “slight increase” in viscosity in thecontext of this application means that adding this polymer to aninventive composition (or water) increases the viscosity of thecomposition (or water) by about 2000 mPa·s to about 50000 mPa·s, moretypically by about 5000 mPa·s to about 40000 mPa·s (using Method A).

“Easy removal” means the composition may be substantially removed with anon-harsh remover, such as water and/or with a water-based cleansingsolution, and without excessive rubbing.

“Emulsifier or emulsifying surfactant” is a term of art that is wellknown to those skilled in the art. See, e.g.http://pharmlabs.unc.edu/labs/emulsions/agents.htm. It is a compoundthat has a hydrophilic part and a lipophilic part (“amphiphilic”) andfacilitates the dispersion of two mutually insoluble phases, in thiscase the dispersion of a liquid fatty substance in water.

“High color intensity” means dramatic visual impact of the tint, in thisinstance, the blackness of the compositions and/or eye lids.

“High shear rate,” as measured on a TA Instrument G2 Rheometer with a 20mm 2° cone in continuous mode (“Method A”), means from 950 s-1 to 1000s-1.

“Low shear rate,” as measured on a TA Instrument G2 Rheometer with a 20mm 2° cone in continuous mode (Method A), means from 0 s-1 to 0.15 s-1.

“Non-associative thickening polymers” or “non-associative thickeners”are typically high molecular weight (greater than about 10⁵ g/mol toabout 10⁸ g/mol) water soluble polymers having a relatively uniformbackbone that lacks hydrophobic modification.

“Synthetic” means synthetically derived.

“Thickener” is term that is well known to a skilled artisan. It means acompound or composition that increases the viscosity or resistance toflow of a composition to which it is added. See, Paint & Coating TestingManual, 14^(th) Edition (J V Koleske Ed., 1995), pp. 268-288;WO2011/076792. A thickening polymer is thus a thickener that is apolymer.

As used herein, all ranges provided are meant to include every specificrange within, and combination of subranges between, the given ranges.Thus, a range from 1-5, includes specifically 1, 2, 3, 4 and 5, as wellas subranges such as and 2-5, 3-5, 2-3, 2-4, 1-4, etc.

Unless otherwise specified herein, all percentages and ratios ofcomponents are by weight relative to the total weight of the finalcomposition.

The viscosity of the gels were also measured at 25° C. with a Rheomat180 viscometer at 200 rmp (revolutions per minute) using a No. 4 or 5spindle (hereinafter, “Method B”). Using this instrument the viscosityis preferably greater than or equal to 5 Pa·s, preferably from about 5Pa·s to about 65 Pa·s, most typically from about 5 to about 60 Pa·s,including all ranges and subranges therebetween. When the compositionincludes waxes, the viscosity trends to the higher ranges with the upperrange closer to 60 Pa·s. When no waxes are present, the viscosity islower, with an upper viscosity range closer to about 35 Pa·s. Theviscosity was measured 10 minutes after switching on the rotation of thespindle.

While the gels of the invention remain pseudoplastic, that is theviscosity of the gels is higher at low shear rate and decreases withincreasing shear rate during a steady shear or continuous flow, the useof applicants' dual-agent viscosity increasing system in oil-in-wateremulsions or water-based dispersions affords comparable non-Newtonianrheology to that displayed by anhydrous compositions or by compositionshaving only a single viscosity increasing agent. By displaying thisnon-Newtonian rheology, the compositions of the invention affordimproved setting, reduced sag and enhanced flow during application ofthe compositions.

The gels of the invention display a particular viscosity ranging from2,000 Pa·s to 90,000 Pa·s at low shear rate and from 0.01 Pa·s to 3 Pa·sat high shear rate (using Method A) and have slopes from about 0.5 toabout 1.0, most preferably 0.6 to about 1.0. The slope referred toherein is the slope of viscosity (Pa·s) versus shear rate (1/s) graph.This viscosity profile is unique in that it affords a water-based gelsystem that mimics the viscosity profile of several different types ofanhydrous gel systems.

In the gels of the invention, the combination of the syntheticassociative thickening polymer and the non-associative thickeningpolymer in a particular ratio, or the associative polymer alone,together with the emulsifier unexpectedly increased the viscosity of theresulting composition at low shear by at least 2000 Pas as measured on aTA Instrument G2 Reheometer with a 20 mm 2° cone in continuous or steadystate mode.

Throughout this application, the shear rate applied to the gels at “lowshear” is from about 0.01 s-1 to about 1 s-1. The shear rate applied tothe gels at “high shear” is from about 900 s-1 to about 1000 s-1.

The pH of the gels of the invention at 25° C. ranges from about 4.5 toabout 8, preferably from about 6 to about 7, typically about 6.0+/−0.3,including all ranges and subranges therebetween.

In an embodiment, the invention relates to a water-based gel cosmeticcomposition comprising:

-   -   (a) a viscosity increasing system comprising (I) at least one        synthetic non-associative thickening polymer; and (II) at least        one synthetic associative thickening polymer;    -   (b) at least one emulsifier;    -   (c) at least one liquid fatty substance;    -   (d) water;    -   (e) optionally a pigment; and    -   (f) optionally at least one wax;        wherein the composition has a viscosity of from about 2,000 Pa·s        to about 90,000 Pa·s at low shear rate as measured on a TA        instrument G2 Rheometer.

Embodiments wherein ratio of non-associative thickener to associativethickener is greater than 1:1

In an embodiment, the invention relates to a water-based gel cosmeticcomposition comprising:

-   -   (a) a viscosity increasing system comprising (I) at least one        synthetic non-associative thickening polymer; and (II) at least        one synthetic associative thickening polymer;    -   (b) at least one emulsifier;    -   (c) at least one liquid fatty substance;    -   (d) water;    -   (e) optionally a pigment; and    -   (f) optionally at least one wax;        wherein the ratio of the at least one synthetic non-associative        thickening polymer (a)(I) to the at least one synthetic        associative thickening polymer (a)(II) is greater than 1:1; all        percentages and ratios being based on the total weight of the        composition.

In another embodiment, the invention relates to a water-based gelcosmetic composition comprising:

-   -   (a) from about 0.11% to about 4% by weight of a viscosity        increasing system comprising (I) from about 0.01% to about 2.0%        by weight of at least one synthetic non-associative thickening        polymer; and (II) from about 0.1% to about 2.0% by weight of at        least one synthetic associative thickening polymer;    -   (b) from about 0.1% to about 7.5% by weight at least one        emulsifier;    -   (c) from about 0.1% to about 30% by weight of a liquid fatty        substance;    -   (d) from about 5% to about 60% by weight water;    -   (e) optionally, at least one pigment; and    -   (f) optionally at least one wax        wherein the ratio of the at least one synthetic non-associative        thickening polymer (a)(I) to the at least one synthetic        associative thickening polymer (a)(II) is greater than 1:1, and        wherein the weight percent of each component is based on the        total weight of the composition.

In the preceding embodiment, the ratio of the at least one syntheticnon-associative thickening polymer (a)(I) to the at least one syntheticassociative thickening polymer (a)(II) is preferably from about 1.5:1 toabout 3:1, more preferably about 2:1.

In another embodiment the emulsifier comprises at least one geminisurfactant. In a particular embodiment, the gemini surfactant is presentin an amount of from about 0.1% to about 1.0% by weight, based on thetotal weight of the composition.

In another embodiment, the invention relates to a water-based gelcosmetic composition comprising:

-   -   (a) from about 0.11% to about 4% by weight of a viscosity        increasing system comprising (I) from about 0.01% to about 2.0%        by weight of at least one synthetic non-associative thickening        polymer; and (II) from about 0.1% to about 2.0% by weight of at        least one associative thickening polymer;    -   (b) from about 0.1% to about 1.0% by weight at least one gemini        surfactant;    -   (c) from about 0.1% to about 30% by weight of at least one        liquid fatty substance;    -   (d) from about 5% to about 60% by weight water;    -   (e) optionally, at least one pigment; and    -   (f) optionally, at least one wax;        wherein the ratio of the at least one synthetic non-associative        thickening polymer (a)(I) to the at least one synthetic        associative thickening polymer (a)(II) is greater than 1:1, said        composition having a viscosity of from about 2,000 Pa·s to about        90,000 Pa·s at low shear rate and from about 0.1 Pa·s to about 3        Pa·s at high shear rate (Method A); all percentages and ratios        being based on the total weight of the composition.

In the immediately foregoing embodiment, if wax is absent, the viscositytends to be in the lower range, typically between 2,000 Pa·s to about60,000 s at low shear rate (Method A), while if wax is present, theviscosity is on the higher range, typically from about 8,000 Pa·s toabout 90,000 Pa·s at low shear rate (Method A).

In a preferred embodiment of the invention the at least one syntheticnon-associative thickening polymer (a)(I) is present in an amount ofabout 1% by weight, the at least one synthetic associative thickeningpolymer (a)(II) is present in an amount of about 0.5% by weight, the atleast one emulsifier (b) is present in an amount of about 0.75% byweight, the at least one liquid fatty substance (c) is present in anamount of about 11.5% by weight, and water (d) is present in an amountof from about 40% to about 55% by weight, relative to the weight of thefinal composition. Embodiments wherein ratio of non-associativethickener to associative thickener is less than or equal to 1:1

In an embodiment, the invention relates to a water-based gel cosmeticcomposition comprising:

-   -   (a) a viscosity increasing system comprising (I) at least one        synthetic non-associative thickening polymer; and (II) at least        one synthetic associative thickening polymer;    -   (b) at least one emulsifier;    -   (c) at least one liquid fatty substance;    -   (d) water;    -   (e) optionally a pigment; and    -   (f) optionally at least one wax;        wherein the ratio of the at least one synthetic non-associative        thickening polymer (a)(I) to the at least one synthetic        associative thickening polymer (a)(II) is less than or equal to        1:1; all percentages and ratios being based on the total weight        of the composition.

In the above embodiment, the non-associative thickening polymer may beabsent (0%).

In another embodiment, the invention relates to a water-based gelcosmetic composition comprising:

-   -   (a) from about 0.11% to about 4% by weight of a viscosity        increasing system comprising (I) from about 0.0% to about 2.0%        by weight of at least one synthetic non-associative thickening        polymer; and (II) from about 0.01% to about 2.0% by weight of at        least one synthetic associative thickening polymer;    -   (b) from about 0.4% to about 7.5% by weight at least one        emulsifier;    -   (c) from about 0.1% to about 30% by weight of a liquid fatty        substance;    -   (d) from about 5% to about 60% by weight water;    -   (e) optionally, at least one pigment; and    -   (f) optionally at least one wax        wherein the ratio of the at least one synthetic non-associative        thickening polymer (a)(I) to the at least one synthetic        associative thickening polymer (a)(II) is less than or equal to        1:1; and wherein the weight percent is based on the total weight        of the composition.

In the immediately preceding embodiment, the ratio of the at least onesynthetic non-associative thickening polymer (a)(I) to the at least onsynthetic associative thickening polymer (a)(II) is from about 0:0.5 toabout 1:3, more preferably about 1:2.

In another embodiment the emulsifier comprises at least one geminisurfactant. In a particular embodiment, the gemini surfactant is presentin an amount of from about 0.1% to about 1.0% by weight, based on thetotal weight of the composition.

In another embodiment, the invention relates to a water-based gelcosmetic composition comprising:

-   -   (a) from about 0.11% to about 4% by weight of a viscosity        increasing system comprising (I) from about 0.1% to about 2.0%        by weight of at least one synthetic non-associative thickening        polymer; and (II) from about 0.01% to about 2.0% by weight of at        least one associative thickening polymer;    -   (b) from about 0.1% to about 1.0% by weight at least one gemini        surfactant;    -   (c) from about 0.1% to about 30% by weight of at least one        liquid fatty substance;    -   (d) from about 5% to about 60% by weight water;    -   (e) optionally, at least one pigment; and    -   (f) optionally, at least one wax;        wherein the ratio of the at least one synthetic associative        thickening polymer (a)(II) to the at least one synthetic        non-associative thickening polymer (a)(I) is equal to or greater        than 1:1, said composition having a viscosity of from about        3,000 Pa·s to about 90,0000 Pa·s at low shear rate and from        about 0.01 Pa·s to about 3 Pa·s at high shear rate (using Method        A); all percentages and ratios being based on the total weight        of the composition.

In the immediately preceding embodiment, if wax is absent, the viscositytends to be on the lower range, typically from about 3,000 Pa·s to about60,000 Pa·s at low shear (Method A), while if wax is present theviscosity is on the higher range, typically from about 9,000 Pa·s toabout 90,000 Pa·s

In a preferred embodiment the at least one synthetic non-associativethickening polymer (a)(I) is present in an amount of from about 0% toabout 1.5% by weight, the at least one synthetic associative thickeningpolymer (a)(II) is present in an amount of from about 1.0% to about 1.5%by weight, the at least one emulsifier (b) is present in an amount ofabout 0.75% by weight, the at least one liquid fatty substance (c) ispresent in an amount of about 11.5% by weight, and water (d) is presentin an amount of from about 46% to about 48% by weight, relative to theweight of the final composition.

In another embodiment, ° the invention relates to a water-based gelcosmetic composition comprising:

-   -   (a) from about 0.1% to about 1.5% by weight of at least one        associative thickening polymer;    -   (b) from about 0.1% to about 1.0% by weight at least one gemini        surfactant;    -   (c) from about 0.1% to about 30% by weight of at least one        liquid fatty substance;    -   (d) from about 5% to about 60% by weight water;    -   (e) optionally, at least one pigment; and    -   (f) optionally, at least one wax;        said composition having a viscosity of from about 4,000 Pa·s to        about 90,000 Pa·s at low shear rate and from about 0.01 Pa·s to        about 3 Pa·s at high shear rate (Method A); all percentages and        ratios being based on the total weight of the composition.

In the above embodiment the associative thickening polymer is typicallypresent in an amount from about 0.1% to about 1.5% by weight, preferablyfrom about 0.2% to about 1.1% by weight, more particularly from about0.5% to about 1.1% by weight, relative to the weight of the composition.

In the immediately preceding embodiment, if wax is absent, the viscositytends to be on the lower range, typically from about 4,000 Pa·s to about60,000 Pa·s at low shear (Method A), while if wax is present theviscosity is on the higher range, typically from about 10,000 Pa·s toabout 90,000 Pa·s at low shear rate (Method A).

In any and all of the foregoing embodiments, the composition may furthercomprises an emollient. When present, the emollient comprises from about0.1% to about 20% by weight, based on the total weight of thecomposition.

In another embodiment, the invention relates to a method of improving aproperty selected from freshness, long wear, comfort, gentleapplication, color intensity, ease of removal, water and/oroil-resistance, adhesion, malleability and transfer resistance of a geleyeliner by incorporating in said eyeliner a synthetic non-associativethickening polymer, and a synthetic associative thickening polymer.

In another embodiment, the invention relates to a method of making up akeratinous substance, in particular the eyes, with the above describedcosmetic composition.

In an embodiment, the synthetic non-associative thickening polymer isammonium polyacryloyldimethyl taurate (“AMPS”, available from Clariant,or from Hoechst under the name Hostacerin AMPS).

In an embodiment, the synthetic associative thickening polymer isammonium acryloyldimethyltaurate/steareth-8 methacrylate copolymer(available from Clariant).

In another embodiment, the emulsifier is a gemini surfactant selectedfrom disodium ethylene dicocamide PEG-15 disulfate. In a preferredembodiment the gemini surfactant is part of a co-emulsifier systemcomposed of behenyl alcohol (and) glyceryl stearate (and) disodiumethylene dicocamide peg-15 disulfate (and) glyceryl stearate citrate(commercially available from Sasol as CERALUTION® H).

Thickening Polymers (a)

The synthetic thickening polymers useful in the practice of embodimentsof the disclosure include those conventionally used in cosmetics.Representative synthetic thickening polymers include synthetic viscosityincreasing polymers and synthetic rheology increasing polymers.

The viscosity increasing system (a) is present in the composition of theinvention in an amount of from about 0.11% to about 4.0% by weight,typically from about 0.3% to about 3.0% by weight, more typically fromabout 0.5% to about 2.15% by weight, more particularly from about 0.8%to about 1.5%, by weight, including all ranges and subrangestherebetween, all weights being based on the total weight of thecomposition.

The gel compositions of the invention may be in the form of an oil inwater emulsion.Synthetic Non-Associative Polymers (a)(I)

These typically high molecular weight polymers increase viscosity whendissolved in the continuous phase by occupying a large volume andimmobilizing the continuous phase in the polymer network. See, e.g.,Paint & Coating Testing Manual, 14^(th) Edition (J V Koleske Ed., 1995),pp. 268-288; and WO2011/076792. Non-limiting examples of hydrophilicthickeners include modified or unmodified carboxyvinyl polymers, such asthe products sold under the name CARBOPOL (CTFA name: carbomer) byGoodrich, homopolymers or copolymers of acrylic or methacrylic acids orthe salts thereof and the esters thereof, polyacrylates andpolymethacrylates such as the products sold under the names LUBRAJEL andNORGEL by Guardian, or under the name HISPAJEL by Hispano Chimica, andpolyacrylic acids of SYNTHALEN K type, polyacrylamides, copolymers ofacrylic acid and of acrylamide sold in the form of the sodium saltthereof, such as under the names RETEN® by Hercules, the sodiumpolymethacrylate such as sold under the name DARVAN 7® by Vanderbilt,and the sodium salts of polyhydroxycarboxylic acids, optionallycrosslinked and/or neutralized 2-acrylamido-2-methylpropanesulphonicacid polymers and copolymers, for instancepoly(2-acrylamido-2-methylpropanesulphonic acid) such as sold byClariant under the name HOSTACERIN AMPS (CTFA name: ammoniumpolyacryldimethyltauramide), crosslinked anionic copolymers ofacrylamide and of AMPS, e.g. in the form of a water-in-oil emulsion,such as those sold under the name SEPIGEL™ 305 (CTFA name:Polyacrylamide/C13-14 Isoparaffin/Laureth-7) and under the nameSIMULGEL™ 600 (CTFA name: Acrylamide/Sodium acryloyldimethyltauratecopolymer/Isohexadecane/Polysorbate 80) by SEPPIC, polyacrylic acid(available commercially as Carbomers) and acrylates copolymers such assodium polyacrylate and polyacryloyldimehtyl taurate, and mixtures ofthese.

Particularly useful synthetic non-associative thickening polymersinclude sodium acryloyldimethyltaurate/VP crosspolymer, acrylatescopolymer, sodium polyacrylate, ammonium acryloyldimethyltaurate/carboxyethyl acrylate crosspolymer, ammoniumpolyacryloyldimethyl taurate, ammonium acryloyldimethyltaurate/vinylformamide copolymer, ammonium polyacryloyldimethyl taurate/ammoniumpolyacryldimethyltauramide and ammonium acryloyldimethyltaurate/VPcopolymer, and mixtures thereof.

In a preferred embodiment, the synthetic non-associative thickeningpolymer is ammonium polyacryloyldimethyl taurate.

In an embodiment, the synthetic non-associative polymer (a)(I) ispresent in the composition of the invention in an amount of from about0.01% to about 2.0% by weight, typically from about 0.1% to about 1.5%by weight, more typically from about 0.5% to about 1.25% by weight, moreparticularly about 1% by weight, including all ranges and subrangestherebetween, all weights being based on the total weight of thecomposition. In this embodiment, the ratio of (a)(I) to (a)(II) isgreater than 1:1.

In another embodiment, the synthetic non-associative polymer (a)(I) ispresent in the composition of the invention in an amount of from about0.1% to about 2.0%, typically from about 0.1% to about 1.5%, moretypically from about 0.3% to about 1.25%, more particularly about 0.5%,by weight, including all ranges and subranges therebetween, all weightsbeing based on the total weight of the composition. In this embodiment,the ratio of (a)(I) to (a)(II) is equal to or less than 1:1.

In another embodiment, the synthetic non-associative polymer (a)(I) ispresent in the composition of the invention at 0%, by weight, based onthe total weight of the composition. In this embodiment, the at leastone synthetic associative thickening polymer (a)(II) is the solesynthetic thickening polymer.

Synthetic Associative Thickening Polymer (a)(II)

Synthetic associative thickening polymers are non-crosslinked orcrosslinked polymers that are capable of non-specific hydrophobicassociations due to polymers' hydrophobic modification. Thesehydrophobic associations are chiefly responsible for the increase inviscosity observed with these thickeners. See Paint & Coating TestingManual, 14^(th) Edition (J V Koleske Ed., 1995), pp. 268-288. In thecurrent invention, the synthetic associative thickening polymers usedunexpectedly modified the rheology profile of the resulting compositionto afford high pseudoplasticity (that is increased flowability of thecompositions at high shear and enhanced product pick-up). Further,incorporation of these polymers resulted in compositions having a largerslope in the corresponding viscosity (Pa·s) versus shear rate (1/s)graph as determined on a TA Instrument G2 Rheometer with a 20 mm 2° conein continuous or steady state mode. Examples of such polymers areprovided in U.S. Pat. No. 7,220,408, which is herein incorporated byreference. See, also, Paint & Coating Testing Manual, 14^(th) Edition (JV Koleske Ed., 1995), pp. 268-288.

The synthetic associative polymers in accordance various exemplaryembodiments may be anionic, cationic, nonionic or amphoteric. By way ofexample, synthetic associative polymers which may be chosen includethose comprising at least one hydrophilic unit and at least onefatty-chain allyl ether unit, such as those in which the hydrophilicunit is constituted of an ethylenic unsaturated anionic monomer, such asa vinylcarboxylic acid or an acrylic acid, a methacrylic acid, andmixtures thereof, and in which the fatty-chain allyl ether unitcorresponds to the monomer of formula (I) below:

CH₂═C(R′)CH₂OB_(n)R  (I)

in which R′ is chosen from H or CH₃, B is chosen from an ethyleneoxyradical, n is zero or is chosen from an integer ranging from 1 to 100,and R is chosen from a hydrocarbon-based radical chosen from alkyl,arylalkyl, aryl, alkylaryl and cycloalkyl radicals containing from 8 to30 carbon atoms, such as from 10 to 24 carbon atoms, or from 12 to 18carbon atoms. Exemplary and non-limiting polymers of this type aredescribed and prepared, according to an emulsion polymerization process,in patent EP 0 216 479.

Non-limiting examples of synthetic associative anionic polymers that mayalso be chosen include anionic polymers comprising at least onehydrophilic unit of olefinic unsaturated carboxylic acid type, and atleast one hydrophobic unit exclusively of (C₁₀-C₃₀)alkyl ester ofunsaturated carboxylic acid type. Examples that may be mentionedinclude, but are not limited to, the anionic polymers described andprepared according to U.S. Pat. Nos. 3,915,921 and 4,509,949, which areherein incorporated by reference.

Cationic associative polymers that may be chosen include, but are notlimited to, polyacrylates containing amine side groups.

Exemplary non-ionic associative polymers include copolymers ofvinylpyrrolidone and of fatty-chain hydrophobic monomers, for instanceAntaron® or Ganex® V216 (vinylpyrrolidone/hexadecene copolymers);Antaron® or Ganex® V220 (vinylpyrrolidone/eicosene copolymers), sold bythe company I.S.P., copolymers of C₁-C₆ alkyl methacrylates or acrylatesand of amphiphilic monomers comprising at least one fatty chain, andcopolymers of hydrophilic methacrylates or acrylates and of hydrophobicmonomers comprising at least one fatty chain, for instance thepolyethylene glycol methacrylate/lauryl methacrylate copolymer; polymerswith an aminoplast ether skeleton containing at least one fatty chain,such as the Pure Thix® nonionic associative water phase thickeners soldby the company Southern Clay Products, Inc.

Associative polyurethanes may also be chosen in various exemplary andnon-limiting embodiments. These are nonionic block copolymers comprisingin the chain both hydrophilic blocks usually of polyoxyethylene nature,and hydrophobic blocks that may be aliphatic sequences alone and/orcycloaliphatic and/or aromatic sequences. Associative polyurethanescomprise at least two hydrocarbon-based lipophilic chains containingfrom C₆ to C₃₀ carbon atoms, separated by a hydrophilic block, thehydrocarbon-based chains optionally being pendent chains or chains atthe end of a hydrophilic block. For example, it is possible for one ormore pendent chains to be provided. In addition, the polymer maycomprise a hydrocarbon-based chain at one or both ends of a hydrophilicblock. The associative polyurethanes may be arranged in triblock ormultiblock form. The hydrophobic blocks may thus be at the each end ofthe chain (for example, triblock copolymer with a hydrophilic centralblock) or distributed both at the ends and within the chain (forexample, multiblock copolymer). These polymers may also be graftpolymers or starburst polymers. For example, the associativepolyurethanes may be triblock copolymers in which the hydrophilic blockis a polyoxyethylene chain containing from 50 to 1000 oxyethylenegroups.

By way of non-limiting example, associative polymers of the polyurethanepolyether type that may be used include the polymer C₁₆-OE₁₂₀-C₁₆ fromServo Delden (under the name SER AD FX1100), which is a moleculecontaining a urethane function and having a weight-average molecularweight of 1300), OE being an oxyethylene unit, Nuvis® FX 1100 (Europeanand US INCI name “Steareth-100/PEG-136/HMDI Copolymer” sold by thecompany Elementis Specialties), and also Acrysol RM 184® (sold by thecompany Rohm and Haas). Further exemplary associative polymers that maybe chosen include RHEOLATE® 205 containing a urea function, sold byRheox, or RHEOLATE® 208 or 204, or RHEOLATE® FX1100 from Elementis. Theproduct DW 1206B from Rohm & Haas containing a C₂₀ alkyl chain with aurethane bond, sold at a solids content of 20% in water, may also beused.

In further exemplary embodiments, solutions or dispersions of theabove-mentioned polymers, especially in water or in water-alcoholmedium, may be chosen. Examples of such polymers include SER AD FX1010,SER AD FX1035 and SER AD 1070 from Servo Delden, and RHEOLATE® 255,RHEOLATE® 278 and RHEOLATE® 244 sold by Rheox. Further examples includethe products ACULYN™ 46, DW 1206F and DW 1206J, and also ACRYSOL RM 184or ACRYSOL 44 from Rohm & Haas, and BORCHIGEL LW 44 from Borchers.

Additional associative thickening polymers include polyacrylicacid/alkyl acrylate copolymers of PEMULEN type; PEG-150/stearylalcohol/SMDI copolymer such as that sold under the name ACULYN™ 46 byRohm & Haas; steareth-100/PEG-136/HDI copolymer such as sold under thename RHEOLATE® FX 1100 by Elementis).

Mixtures of the above associative polymers are also contemplated hereinas useful in the invention.

As used herein, the term “copolymers” is intended to mean bothcopolymers obtained from two types of monomers and those obtained frommore than two types of monomers, such as, for example, terpolymersobtained from three types of monomers. The chemical structure of thecopolymers comprises at least one hydrophilic unit and at least onehydrophobic unit. The expression “hydrophobic unit” or “hydrophobicunit” is understood to mean a radical possessing a saturated orunsaturated and linear or branched hydrocarbon-based chain whichcomprises at least 8 carbon atoms, for example from 10 to 30 carbonatoms, as a further example from 12 to 30 carbon atoms, and as yet afurther example from 18 to 30 carbon atoms.

In certain exemplary and non-limiting embodiments, the associativethickening copolymers are chosen from the copolymers resulting from thepolymerization of:

(1) at least one monomer of formula (II):

CH2═CH(R1)COOH  (II)

wherein R₁ is chosen from H or CH₃ or C₂H₅, providing acrylic acid,methacrylic acid, or ethacrylic acid monomers, and (2) at least onemonomer of (C₁₀-C₃₀)alkyl ester of unsaturated carboxylic acid typecorresponding to the monomer of formula (III):

CH2═CH(R2)COOR3  (III)

wherein R₂ is chosen from H or CH₃ or C₂H₅, providing acrylate,methacrylate or ethacrylate units, R₃ denoting a C₁₀-C₃₀ alkyl radical,such as a C₁₂-C₂₂ alkyl radical.

Non-limiting examples of (C₁₀-C₃₀)alkyl esters of unsaturated carboxylicacids are for example chosen from lauryl acrylate, stearyl acrylate,decyl acrylate, isodecyl acrylate, dodecyl acrylate and thecorresponding methacrylates, such as lauryl methacrylate, stearylmethacrylate, decyl methacrylate, isodecyl methacrylate and dodecylmethacrylate, and mixtures thereof.

Additionally, crosslinked thickening polymers may be chosen according tofurther exemplary embodiments. For example, such polymers may be chosenfrom polymers resulting from the polymerization of a mixture of monomerscomprising:

-   -   acrylic acid,    -   an ester of formula (III) described above, in which R₂ is chosen        from H or CH₃, R₃ denoting an alkyl radical having from 12 to 22        carbon atoms, and    -   a crosslinking agent, which is a well-known copolymerizable        polyethylenic unsaturated monomer, such as diallyl phthalate,        allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol        dimethacrylate and methylenebisacrylamide.

By way of example, crosslinked thickening polymers comprising about 60%to about 95% by weight of acrylic acid (hydrophilic unit), about 4% toabout 40% by weight of C₁₀-C₃₀ alkyl acrylate (hydrophobic unit), andabout 0% to about 6% by weight of crosslinking polymerizable monomer. Inyet further embodiments, the crosslinked thickening polymers maycomprise about 96% to about 98% by weight of acrylic acid (hydrophilicunit), about 1% to about 4% by weight of C₁₀-C₃₀ alkyl acrylate(hydrophobic unit), and about 0.1% to 0.6% by weight of crosslinkingpolymerizable monomer, such as those described above. Examples of suchpolymers include acrylate/C₁₀-C₃₀ alkyl acrylate copolymers (INCI name:Acrylates/C10-30 Alkyl Acrylate Crosspolymer), such as the products soldby Lubrizol under the trade names PEMULEN™ TR1, PEMULEN™ TR2, CARBOPOL®1382 and CARBOPOL® EDT 2020 may be chosen.

In further embodiments, the at least one synthetic associativethickening polymer may be chosen from nonionic homopolymers orcopolymers containing ethylenically unsaturated monomers of the esterand/or amide type. For example, the products sold under the namesCYANAMER P250 by the company CYTEC (polyacrylamide), methylmethacrylate/ethylene glycol dimethacrylate copolymers (such as PMMAMBX-8C by the company US COSMETICS), butyl methacrylate/methylmethacrylate copolymers (such as ACRYLOID B66 by the company RHOM HMS),and polymethyl methacrylates (BPA 500 by the company KOBO) may bechosen.

Further non-limiting examples of synthetic associative thickeningpolymers include polyacrylamide (and) C13-14 isoparaffin (and) laureth-7(such as Sepigel™ 305 from Seppic), acrylates/C10-30 alkyl acrylatecrosspolymer (such as Carbopol® Ultrez 20 polymer from Lubrizol),acrylates/C10-30 alkyl acrylate crosspolymer (such as Permulen™ TR-1from Lubrizol), and polyacrylate crosspolymer-6 (such as Sepimax Zenfrom Seppic).

In a preferred embodiment, the associative thickening polymers includecross- or co-polymers of polyacryloyl/taurate orpolyacryloyl/dimethyltaurate. Non-limiting examples of such polymersinclude ammonium acryloyldimethyltaurate/steareth-25 methacrylatecrosspolymer, ammonium acryloyldimethyltaurate/steareth-8 methacrylatecopolymer, ammonium acryloyldimethyltaurate/beheneth-25 methacrylatecrossopolymer, and ammonium acryloyldimethyltaurate/laureth-methacrylatecopolymer, and mixtures thereof.

Additional non-limiting examples of useful associative thickeningpolymers include acrylates/vinyl neodecanoate crosspolymer,acrylates/steareth-20 methacrylate crosspolymer, and peg-150/stearylalcohol/SMDI copolymer, and mixtures thereof.

In an embodiment, the associative thickening polymer is also a hydratingagent. A non-limiting example of a synthetic associative thickeningpolymer that is also a hydrating agent is ammoniumacryloyldimethyltaurate/steareth-8 methacrylate copolymer.

The synthetic associative thickening polymer (a)(II) is present in thecomposition of the invention in an amount of from about 0.1% to about2.0%, typically from about 0.2% to about 1.5%, more typically from about0.3% to about 0.9%, more particularly about 0.5%, by weight, includingall ranges and subranges therebetween, all weights being based on thetotal weight of the composition. In this embodiment, the ratio of (a)(I)to (a)(II) is greater than 1:1.

In another embodiment of the invention, the synthetic associativethickening polymer (a)(II) is present in the composition of theinvention in an amount of from about 0.1% to about 2.0%, typically fromabout 0.2% to about 1.5%, more typically from about 0.5% to about 1.5%,more particularly from about 0.5% to about 1.1%, by weight, includingall ranges and subranges therebetween, all weights being based on thetotal weight of the composition. In this embodiment of the invention,the ratio of (a)(I) to (a)(II) is equal to or less than 1:1. In thisembodiment (a)(I) can be as low as 0%.

In an embodiment of the invention, the ratio of the at least onesynthetic non-associative thickening polymer (a)(I) to the at least onesynthetic associative thickening polymer (a)(II) is greater than 1:1,more particularly from about 1.5:1 to about 3:1, even more particularlyfrom about 1.5:1 to about 2.5:1, most preferably about 2:1, by weight,based on the weight percent of each surfactant in the final composition.

In a second embodiment of the invention, the ratio of the at least onesynthetic non-associative thickening polymer (a)(I) to the at least onsynthetic associative thickening polymer (a)(II) is less than 1:1, moreparticularly from about 0:1.5 to about 1:3, even more preferably about1:2.

When anionic thickening polymers are used, they may be neutralizedbefore being included in or as they are added to the compositions of thedisclosure. Such anionic thickening polymers may be neutralized byemploying traditional neutralizing agents such as alkanolamines, forexample, monoethanolamine and diethanolamine; aminomethyl propanol;basic amino acids, for example arginine and lysine; and ammoniumcompounds and their salts.

Emulsifier (b)

The compositions of the invention contain at least one emulsifier chosenfrom amphoteric, anionic, cationic and nonionic emulsifiers, used aloneor as a mixture. The emulsifiers are appropriately chosen according tothe emulsion to be obtained (e.g. W/O or O/W).

Emulsifiers that may be used for the preparation of the W/O emulsions,include sorbitan, glycerol or sugar alkyl esters or ethers; siliconesurfactants, for instance dimethicone copolyols, such as the mixture ofcyclomethicone and of dimethicone copolyol (sold under the name DC 5225C by the company Dow Corning), and alkyldimethicone copolyols such aslaurylmethicone copolyol (sold under the name Dow Corning 5200Formulation Aid by the company Dow Corning); cetyldimethicone copolyol(e.g. the product sold under the name Abil EM 90R by the companyEvonik), and the mixture of cetyldimethicone copolyol, of polyglycerylisostearate (4 mol) and of hexyl laurate (e.g. product sold under thename Abil WE O9 by the company Evonik). One or more co-emulsifiers mayalso be added thereto, which may be chosen for example from the groupcomprising polyol alkyl esters.

Non-limiting examples of useful polyol alkyl esters include polyethyleneglycol esters, for instance PEG-30 dipolyhydroxystearate, such as theproduct sold under the name Arlacel P135 by the company Croda.

Glycerol and/or sorbitan esters that may especially be mentionedinclude, for example, polyglyceryl isostearate, such as the product soldunder the name Isolan GI 34 by the company Evonik, sorbitan isostearate,such as the product sold under the name Arlacel 987 by the companyCroda, sorbitan glyceryl isostearate, such as the product sold under thename Arlacel 986 by the company Croda, and mixtures thereof.

Non-limiting examples of emulsifying polyoxyalkylenated siliconeelastomers include those disclosed in U.S. Pat. Nos. 5,236,986,5,412,004, 5,837,793 and 5,811,487, which are herein incorporated byreference. These silicone elastomers are preferably formulated under theform of a gel in a hydrocarbonated and/or a silicone oil. In those gels,the polyoxyalkylenated silicone elastomer is often under the form ofspherical particles.

Examples of polyoxyethylenated silicone elastomers include the followingcompositions:

a) available from Shin Etsu;

-   -   KSG-16 dimethicone (and) dimethicone/vinyl dimethicone        corpsspolymer    -   KSG-21 (at 27% in active material) INCI name: Dimethicone/PEG-10        Dimethicone vinyl dimethicone crosspolymer),    -   KSG-20 (at 95% % in active material) INCI name: PEG-10        Dimethicone Crosspolymer),    -   KSG-30, (at 100% % in active material) INCI name: Lauryl PEG-15        Dimethicone vinyl dimethicone crosspolymer),    -   KSG-31 (at 25% in active material) INCI name: Lauryl PEG-15        Dimethicone vinyl dimethicone crosspolymer),    -   KSG-32 or KSG-42 or KSG-320 or KSG-30 (at 25% in active        material) INCI name: Lauryl PEG-15 Dimethicone vinyl dimethicone        crosspolymer),    -   KSG-33: Lauryl PEG-15 (at 20% in active material) Dimethicone        vinyl dimethicone crosspolymer),    -   KSG-210 (at 25% in active material) INCI name:        Dimethicone/PEG-10/15 crosspolymer),    -   KSG-310: lauryl modified polydimethylsiloxane polyoxyéthylenated        in mineral oil,    -   KSG-330 and KSG-340: PEG-15/lauryl dimethicone crosspolymer    -   X-226146 (at 32% % in active material) INCI name:        Dimethicone/PEG-10 Dimethicone vinyl dimethicone crosspolymer);        and        b) available from Dow Corning:    -   DC9010 (at 9% in active material) and DC9011 (at 11% in active        material) INCI name: PEG-12 dimethicone crosspolymer)    -   DC9040 cyclopentasiloxane (and) dimethicone crosspolymer    -   DC9041 dimethicone (and) dimethicone crosspolymer;        and the like and mixtures thereof.

The above products are typically in the form of oily gel containing theparticles of silicone elastomer.

In an embodiment, KSG-210 is used (INCI name: Dimethicone/PEG-10/15crosspolymer, 25% active silicone elastomer in a silicone oil).

Other silicone elastomers include Polyglycerolated silicone elastomersmay also be used as water/oil emulsifiers. Examples of such compoundsare provided in WO-A-2004/024798.

Specific examples of polyglycerolated silicone elastomers include thefollowing compositions commercially available from Shin-Etsu: KSG-710(at 25% in active material, INCI name: dimethicone/polyglycerin-3crosspolymer); and KSG-820, KSG-830 and KSG-840, all of which aredimethicone/polvaleverin-3 crosspolymer (INCI), but in differentdiluents, 820 is in isododecane, 830 is in triethyl hexanoin and 840 isin squalene.

For oil-in-water (O/W) emulsions, exemplary emulsifiers that may be usedinclude nonionic emulsifiers such as oxyalkylenated (more particularlypolyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fattyacid esters of sorbitan; oxyalkylenated (oxyethylenated and/oroxypropylenated) fatty acid esters, for instance the mixture PEG-100stearate/glyceryl stearate sold, for example, by the company Croda underthe name Arlacel 165; oxyalkylenated (oxyethylenated and/oroxypropylenated) fatty alkyl ethers; sugar esters, for instance sucrosestearate; fatty alkyl ethers of sugars, especially alkyl polyglucosides(APG) such as decylglucoside and laurylglucoside sold, for example, bythe company Cognis under the respective names Plantaren 2000 andPlantaren 1200, cetostearyl glucoside which optionally can be in amixture with cetostearyl alcohol, sold, for example, under the nameMontanov 68 by the company SEPPIC or sold under the name Tegocare CG90by the company Evonik or under the name Emulgade KE3302 sold by thecompany Cognis, and also arachidyl glucoside, for example in the form ofa mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside,sold under the name Montanov 202 by the company SEPPIC. According to aspecific embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol canbe in the form of a self-emulsifying composition, for example asdisclosed in WO-A-92/06778; the hydrophobically modified inulines asInuline Lauryl Carbamate as the product sold under the denominationINUTEC SP1 by the Company Beneo-ORAFTI.

According to a specific embodiment of the invention, the emulsifier is agemini surfactant. Gemini surfactants consist of two conventionalsurfactant molecules (sometimes also referred to as dimers, which can beidentical or different) chemically bonded together by a spacer. The twoterminal hydrocarbon tails are hydrophobic. The two polar heads can becationic, anionic or nonionic and are generally hydrophilic. A varietyof spacers can be used. Such surfactants are described for example inthe following publications: B S Sekhon, Gemini (dimeric) Surfactants—TheTwo-Faced Molecules, RESONANCE (March 2004), pp. 42-49; Milton J. Rosen,Gemini Surfactants, Properties of surfactant molecules with twohydrophilic groups and two hydrophobic groups, Cosmetics & Toiletriesmagazine, vol. 113 (December 1998), pp. 49-55; and Milton J. Rosen,Recent Developments in Gemini Surfactants, Allured's Cosmetics &Toiletries magazine, vol 116, n° 7 (July 2001), pages 67-70. Thesesurfactants are known in the art of cosmetics. They are known to havegood emulsifying properties for the preparation of emulsions, includingoil-in-water (O/W) emulsions. See, e.g., US2005/0724935 (WO 2007/054824,L'Oreal), US2009/0105353 and U.S. Pat. No. 5,863,886, all which areherein incorporated by reference.

According to an embodiment of the invention the emulsifier is an anionicgemini surfactant having the formula (IV)

whereinR¹ and R³ are a C₈-C₂₅ linear alkyl group;R² is a C₂-C₈ alkylene group;X and Y are independently selected from (C₂H₄O)n-RF, where n is 10-15andRF is —SO₃M, wherein M is an alkaline atom.

A preferred gemini surfactant is the anionic compound disodium ethylenedicocamide -PEG-15 disulfate (INCI name, also known as sodium dicocoylethylene diamine PEG-15 sulfate (non INCI name)) having the formula:

The gemini surfactant may be used, for example, as a mixture with othersurfactants or co-emulsifiers, such as for example in the form ofproducts sold by the company Sasol under the trade name Ceralution®. Thefollowing are particularly preferred gemini surfactant- andco-emulsifier-containing compositions:

Ceralution® H: behenyl alcohol, glyceryl stearate, glyceryl stearatecitrate and sodium dicocoylethylenediamine PEG-15 sulfate;Ceralution® F: sodium lauroyl lactylate and sodiumdicocoylethylenediamine PEG-15 sulfate;Ceralution® C: aqua, capric/caprylic triglyceride, glycerin,ceteareth-25, sodium dicocoylethylenediamine PEG-15 sulfate, sodiumlauroyl lactylate, behenyl alcohol, glyceryl stearate, glyceryl stearatecitrate, gum arabic, xanthan gum, phenoxyethanol, methyl paraben, ethylparaben, butyl paraben isobutyl paraben (INCI names).

The preferred embodiment, gemini surfactant is the mixture of behenylAlcohol, Glyceryl Stearate, Glyceryl Stearate Citrate and SodiumDicocoyl ethylenediamine PEG-15 Sulfate (Ceralution® H).

In the Ceralution®-type of surfactant system, the gemini surfactantrepresents from about 3% to about 50% of the weight of these mixtures.

Other emulsifiers or co-emulsifiers that may also be used include fattyesters of citric acid; long chain alcohols, polyols and polyolderivatives, such as for example cetyl alcohol and stearyalcohol;isophthalic acid polymers or sulfo isophthalic acid polymers, andspecifically copolymers of phthalate/sulfo isophthalate/glycol, such asfor example diethyleneglycol/phthalate/isophthalate/1,4-cyclohexane-dimethanol copolymer (INCIname: Polyester-5sol), available from Eastman Chemical under thetradename Eastman AQ® polymer (AQ35S, AQ38S, AQ55S, AQ48 Ultra).

Polyurethane polyether polymers may also be used as emulsifiers.Examples of such polymers include Elfacos® T210® (C12-C14 alkyl chain)and Elfacos® T212® (C18 alkyl chain) sold by Akzo.

In an embodiment the emulsifier is selected from long chain fattyalcohols, fatty esters of polyols, fatty acids, and mixtures thereof.

The emulsifier is present in the composition of the invention in anamount of from about 0.2% to about 7.5%, preferably from about 2% toabout 6%, most preferably about 5%, by weight, including all ranges andsubranges therebetween, all weights being based on the total weight ofthe composition.

Liquid Fatty Substance (c)

The compositions according to the invention contain a liquid fattysubstance which may be selected, for example, from organic solvents andvolatile and/or non-volatile oils, and mixtures thereof. These oilsinclude low viscosity oils (having a viscosity from about 5 to about 10centipoise) and high viscosity oils (having a viscosity of from about100 to about 10,000 centipoise), and mixtures thereof. These fattysubstances are liquid at room temperature.

Representative suitable solvents include non-polar volatilehydrocarbon-based oils include isodecane and isododecane, and forexample, the oils sold under the trade names Isopar™ or Permythyl®.Preferably, the volatile oils have a flash point of at least 40° C.

Other exemplary organic solvents are non-volatile solvents which includepolyalphaolefins such as hydrogenated polydecene, hydrogenated C6-14olefin polymers and polydecene.

Natural oils may also be used so long as they are physiologicallyacceptable. Such oils include hydrocarbon-based plant oils with a hightriglyceride content such as sweet almond oil, avocado oil, olive oil,candlenut oil, vitamin E oil, and the like.

Volatile and non-volatile silicone oils, may also be used. Such oils aredescribed, for example in US 2011/0293550, which to the extent required,is herein incorporated by reference. Suitable silicone oils include, forinstance, volatile or non-volatile polymethylsiloxanes (PDMS) with alinear or cyclic silicone chain, which are liquid or pasty at roomtemperature, especially cyclopolydimethylsiloxanes (cyclomethicones)such as cyclohexasiloxane; polydimethyl-siloxanes comprising alkyl,alkoxy or phenyl groups, which are pendent or at the end of a siliconechain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones,phenyltrimethylsiloxydiphenyl-siloxanes, diphenyl dimethicones,diphenylmethyl-diphenyltrisiloxanes or 2-phenylethyl trimethylsiloxysilicates, and polymethylphenylsiloxanes; and dimethicone fluids havingviscosity values of equal to or greater than 300 cPs; and mixturesthereof.

The fatty substance may also be selected from non-silicone oils such ashydrogenated polyisobutene; and fatty esters such as isostearyl hydroxysterate, glyceryl ethylhexanoate/stearate/adipate, pentaerythrityltetraethylhexanoate, isononyl isononanoate, and isopropyl lauroylsarcosinate; and mixtures thereof.

In a particular embodiment the liquid fatty substance is selected fromdimethicone, dimethicone (and) dimethiconol, phenyl trimethicone,glyceryl ethylhexanoate/stearate/adipate, isostearyl hydroxyl sterate,and mixtures thereof.

The liquid fatty substance (c) is present in the composition of theinvention in an amount of from about 0.1% to about 30%, preferably fromabout 0.5% to about 20%, more particularly from about 1% to about 17%,most particularly about 2% to about 15%, by weight, including all rangesand subranges therebetween, all weights being based on the total weightof the composition.

Water (d)

The compositions for the invention also comprise water in an amountranging from about 5% to about 60%, preferably from about 10% to about55%, most typically from about 40% about 50%, including all ranges andsubranges therebetween, by weight, relative to the total weight of thecompositions.

The compositions of the invention may include additional solvents. Inparticular, the aqueous phase may include at least one organic solventthat is water-miscible. Non-limiting examples of suitable organicsolvents include C₁₋₄ alkanols, such a sethanol and isopropanol;glycerol; glycols and glycol ethers such as 2-butoxyethanol, propyleneglycol, butylene glycol, monomethyl ether of propylene glycol, monethylether and monomethyl ether of diethylene glycol, aromatic alcohols suchas benzyl alcohol and phenoxyethanol; analogous products and mixtures ofthe foregoing products.

Other solvents include caprylic/capric acid triglycerides (such as thosesold under the trade name Miglyol®.

In addition to water, the compositions of the invention may comprise asolvent in an amount ranging from about 0.1% to about 10%, preferablyfrom about 3% to about 6%, including all ranges and subrangestherebetween, by weight, relative to the total weight of thecompositions.

Pigments (e)(Optional)

The cosmetic composition of the invention may optionally include atleast one pigment or dyestuff. Suitable pigments/dyes include, but arenot limited to, pulverulent dyestuffs, liposoluble dyes, water-solubledyes, and pearling agents.

The pulverulent dyestuffs may, for instance, be chosen from pigments andnacres. Useful pigments include titanium dioxide, zirconium oxide, zincoxide, cerium oxide, iron oxide, chromium oxide, manganese violet,ultramarine blue, chromium hydrate, and ferric blue. Non-limitingexamples of organic pigments include carbon black, pigments of D&C type,and lakes based on cochineal carmine, barium, strontium, calcium, andaluminum.

The nacres which may be used include, for example, mica coated withtitanium or with bismuth oxychloride, colored nacreous pigments such astitanium mica with iron oxides, titanium mica with ferric blue orchromium oxide, titanium mica with an organic pigment chosen from thosementioned above, and nacreous pigments based on bismuth oxychloride.

Representative liposoluble dyes which may be used according to thepresent invention include Sudan Red, DC® Red 17, DC® Green 6, beta-carotene, soybean oil, Sudan Brown, DC® Yellow 11, DC®) Violet 2, DC®)Orange 5, annatto, and quinoline yellow.

In an embodiment the pigment is iron oxides.

The at least one pigment/dyestuff may be present in the cosmeticcomposition in an amount ranging from about 5% to about 30%, moreparticularly from about 10% to about 25%, particularly about 20%,including all ranges and subranges therebetween, by weight, relative tothe total weight of the compositions.

Wax (f) (Optional)

While the compositions of the invention optionally may include wax, theyalso may be devoid of waxes (e.g. having less than about 5% wax,preferably 0%).

For the purposes of the present invention, the term “wax” is understoodto mean a lipophilic compound, which is solid at room temperature (25°C.), with a reversible solid/liquid change of state, which has a meltingpoint of greater than or equal to 30° C., which may range up to 120° C.The melting point of the wax may be measured using a differentialscanning calorimeter (DSC), for example the calorimeter sold under thename DSC 30 by Mettler. For waxes that are derived from petroleum, suchas microcrystalline wax, the melting point may be measured according tothe drop ASTM method, D-127.

The waxes may be hydrocarbon-based waxes, fluoro waxes and/or siliconewaxes and may be of plant, mineral, animal and/or synthetic origin. Inparticular, the waxes have a melting point of greater than 25° C. andbetter still greater than 45° C.

Hydrocarbon-based waxes, for instance beeswax, lanolin wax or Chineseinsect wax; rice wax, carnauba wax, candelilla wax, ouricury wax,esparto grass wax, cork fibre wax, sugarcane wax, Japan wax and sumachwax; montan wax, microcrystalline waxes, paraffins and ozokerite,polyethylene waxes, the waxes obtained by Fisher-Tropsch synthesis andwaxy copolymers, and also esters thereof, may be included in thecompositions of the invention.

Also useful are waxes obtained by catalytic hydrogenation of animal orplant oils containing linear or branched C8-C32 fatty chains. Amongthese waxes, mention may especially be made of hydrogenated jojoba oil,isomerized jojoba oil such as the trans-isomerized partiallyhydrogenated jojoba oil manufactured or sold by Desert Whale under thecommercial reference ISO-JOJOBA-50®, hydrogenated sunflower oil,hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolinoil, bis(1,1,1-trimethylolpropane) tetrastearate sold under the nameHEST 2T-4S® by Heterene and bis(1,1,1-trimethylol-propane) tetrabehenatesold under the name HEST 2T-4B® by Heterene.

The wax obtained by hydrogenation of olive oil esterified with stearylalcohol, sold under the name PHYTOWAX® OLIVE 18L57 and the waxesobtained by hydrogenation of castor oil esterified with cetyl alcoholsold under the names PHYTOWAX® RICIN 16L64 and 22L73 by Sophim may alsobe used. Such waxes are described in patent application FR-A-2 792 190,which is herein incorporated by reference.

The at least one wax that may be present invention may also be a polarwax. The expression “polar wax” is understood to mean waxes comprisingin their chemical structure, in addition to carbon and hydrogen atoms,at least one highly electronegative heteroatom, such as 0, N or P.

The wax may also be chosen from silicone waxes and siloxane resin waxes(also known as silsesquioxane resin waxes).

Useful silicone waxes include alkyl or alkoxy dimeticones containingfrom 16 to 45 carbon atoms, and fluoro waxes.

A suitable example of a silsesquioxane resin wax is apropylsilsesquioxane wax substituted with alkyl units having from 9-40carbon atoms, preferably, at least 30 carbon atoms. Propylsilsesquioxanewaxes, are generally described in patent publication WO2005/100444.

If present, the wax of the present invention is chosen from carnaubawax, candelilla wax, natural (or bleached) beeswax, synthetic beeswax,paraffin wax, silicone waxes, and silsesquioxane resin waxes. Assynthetic beeswax, mention may be made of the wax sold under the nameCYCLOCHEM® 326 A by Evonik Goldschmidt (INCI name: Synthetic Beeswax).

Wax can be present in the composition of the invention in an amount offrom about 0.1% to about 15%, preferably from about 5% to about 10%,most typically about 5%, including all ranges and subrangestherebetween, by weight, all weights being based on the total weight ofthe composition.

Emollients (Optional)

The compositions of the invention include one or more emollient and/orhumectants and/or moisturizers (herein “emollients”). These compoundshydrate the keratinous substrate, including the eye lids, and alsoprovide a “wet” texture and shiny look. Emollients are known to skilledartisan. See, e.g. International Cosmetic Ingredient Dictionary andHandbook Vol. 4 (9th ed. 2002), more particularly the emollientsdisclosed on pages 2930-2936. The disclosure of the InternationalCosmetic Ingredient Dictionary and Handbook Vol. 4, pages 2930-2936, ishereby incorporated by reference. Without limitation, the emollientsthat may be used in the compositions of the invention include, forexample: glycerin; glycerol; propylene glycol; butylene glycol; carnaubawax; beeswax; candelilla; ozokerite; paraffin; rice bran wax;microcrystalline wax; polyethylene wax; mineral oil; almond oil; castoroil; sesame oil; hydrogenated polyisobutene; butylene glycol dicapryltedicaprate (commercially available from Sasol as Myglyol®); and mixturesthereof.

In a particular embodiment the emollient is butylene glycol.

The emollient is present in the composition of the invention in anamount of from about 0.1% to about 20%, preferably from about 1% toabout 15%, more particularly from about 3% to about 10%, by weight,including all ranges and subranges therebetween, all weights being basedon the total weight of the composition.

Fillers (Optional)

The cosmetic composition disclosed herein may also comprise at least onefiller commonly used in the art in cosmetic compositions. The fillersmay be lamellar or non-lamellar, inorganic or organic particles.Representative, non-limiting examples of these ingredients include mica,silica, kaolin, iron oxides, titanium dioxide, polyamide powders,polyamide powders, for instance Nylon® (Orgasol from Atochem),poly-alanine powders, polyethylene powders, tetrafluoroethylene polymerpowders, for instance polytetrafluoroethylene(Teflon®, lauroyllysine,starch, boron nitride, hollow polymer microspheres such as those ofpolyvinylidene chloride/acrylonitrile, for instance Expancel® (NobelIndustrie), acrylic powders such as Polytrap® (Dow Corning), polymethylmethacrylate particles and silicone resin microbeads (for example,Tospearls® from Toshiba), methylsilanol/silicate crosspolymer,precipitated calcium carbonate, magnesium carbonate, magnesiumhydrocarbonate, hydroxyapatite, hollow silica microspheres (SilicaBeads® from Maprecos), glass or ceramic microcapsules, metal soapsderived from organic carboxylic acids containing from 8 to 22 carbonatoms, preferably from 12 to 18 carbon atoms, for example, zincstearate, magnesium stearate, lithium stearate, zinc laurate, ormagnesium myristate.

The fillers, if present, are present in amounts generally ranging fromabout 0.1% to about 25%, such as from about 1% to about 20% by weight,relative to the total weight of the composition, including all rangesand subranges therebetween.

Further Additional Components (Optional)

The compositions of the present invention can also include anyadditional ingredient or additive usually used in the field of cosmeticcompositions, in particular eyeliners. For example, these may be chosenfrom, for example, solvents, dispersants, antioxidants (such aspentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate), preservatives(such as for example phenoxyethano, sodium dehydroacetate, disodiumEDTA, caprylyl glycol, and mixtures thereof), fragrances, additionalthickeners or texturizers, liquid lipids/oils, additional viscositymodifiers, additional film formers, sunscreen agents, additionalpigments/colorants/dyes, silica, clays, additional humectants andmoisturizing agents, additional emulsifying agents (e.g. sorbitanoleate), additional structuring agents and fillers, surfactants, shineagents, additional conditioning agents, vitamins, plant extracts,additional film-formers, coalescents/plasticizers, pHmodifiers/neutralizing agents, stabilizers, and mixtures thereof. Anon-exhaustive listing of such ingredients is found in U.S. Pat. No.7,879,316, the entire content of which is hereby incorporated byreference. Additional examples of additives may be found in theInternational Cosmetic Ingredient Dictionary and Handbook (9^(th) ed.2002, and subsequent editions).

Surfactants that may be employed as additional agents may be chosen fromanionic, cationic, nonionic and amphoteric surfactants.

The shine agents may be chosen from silicones, alkoxylated silicones,oils, ethoxylated oils, fats, esters, transesters, hydrocarbons, quatsand mixtures thereof.

Non-limiting examples of shine agents include Amodimethicone,Dimethicone, Dimethiconol, Cyclemethicone, Phenyltrimethicone,Aminopropyl Phenyltrimethicone, Trimethyl Pentaphenyl Trisiloxane, CetylDimethicone, Alkyl Dimethicone, Potassium Dimethicone PEG-7 PantheylPhosphate, Olive oil, Jojoba oil, Apricot oil, Avocado oil, Castor oil,Lanolin, Squalane, Capric/Caprylic Triglyceride, Octyl Palmitate,Isopropyl Palmitate, Isopropyl Myristate, Mineral oil, Petrolatum,Polyquaternium-4, Polyquaternium-11, Behentrimonium Methosulfate,Benetrimonium Chloride and mixtures thereof.

If present in the composition, these additives may constitute from 2% to30%, typically from about 3% to about 15%, and more typically about 7%,including all ranges and subranges therebetween, by weight relative tothe total weight of the composition.

Cosmetic Methods

In an embodiment according to the invention, the compositions comprisinga viscosity increasing system comprising at least one syntheticnon-associative thickening polymer and at least one syntheticassociative thickening polymer, at least one emulsifier, and at leastone liquid fatty substance can provide a water-based gel liner havingone or more the following attributes: a fresh and comfortable feel, longwear, gentle application, color intensity, and ease of removal.Accordingly, another embodiment of the invention provides a method ofmaking up/or enhancing the appearance of eye by applying to the eyelids,topically, the composition of the present invention in a sufficientamount to make up the eyelids. The compositions may be applied to theeyelids as needed, preferably once or twice daily, and then allowed todry before subjecting to contact such as with clothing or other objects.

The compositions according to various exemplary embodiments of theinvention may also have improved and/or increased ease of removability,relative to similar compositions that are not water based. In variousembodiments, ease of removability relates to ease of removing thecomposition from the eyelids with warm (e.g. about 50° C. or higher)water. Optionally, conventional cleansing agents such as soap or make-upremover may also be used.

As such, the disclosure also relates to methods of improving orincreasing the ease of removability of eyeliner compositions byincorporating a synthetic non-associative thickening polymer, such asammonium polyacryloyldimethyl taurate, and a synthetic associativethickening polymer, such as ammonium acryloyldimethyl taurate/steareth-8methacrylate copolymer into said compositions as described herein.

Another embodiment of the invention relates to a method of improving atleast one property selected from long wear, comfort, color intensity,ease of removal, water and/or oil-resistance, shine, adhesion,malleability, transfer resistance and ease of removal properties byincorporating in said eyeliner at least one sucrose fatty acid ester, aco-emulsifier and a viscosity increasing agent as described herein.

The composition according to the present disclosure may be manufacturedby the known processes generally used in cosmetics.

When the composition of the present invention is an eyeliner, thecomposition may be packaged in an applicator product comprising areservoir and a removable cap for closing the reservoir. The cap may,for example, form a leak-tight seal. An example of such an applicator isa pen-type applicator, such as the applicator described in U.S. Pat.Nos. 4,850,727 and 4,974,980, both of which are herein incorporated byreference.

The applicator assembly may also comprise a member for applying thecomposition to eyelid, wherein the applicator member allows thecomposition to be taken up and also allows the composition taken up tobe deposited on the eyelids. This applicator member can be, for example,securely fastened to the cap for leak-tight closure of the assembly.

The applicator assembly may also comprise a draining member (or drainer)for the applicator member, the draining member possibly being securelyfastened to the reservoir. The applicator member may for example, be aneyeliner brush that is well known to those skilled in the art. Such abrush for instance, comprises bristles extending outwardly from and andparallel to core.

Unless otherwise indicated, all numbers used in the specification andclaims are to be understood as being modified in all instances by theterm “about,” whether or not so stated. It should also be understoodthat the precise numerical values used in the specification, includingthe examples and claims, form additional embodiments of the invention,and are intended to include any ranges which can be narrowed to any toend points disclosed within the exemplary ranges and values provided.Efforts have been made to ensure the accuracy of the numerical valuesdisclosed. However, any measured value can inherently contain certainerrors resulting from the standard deviation found in its respectivemeasuring technique.

Examples

The following Examples are intended to be non-restrictive andexplanatory only, with the scope of the invention being defined by theclaims.

Method of Preparation of Inventive Compositions:

The Phases noted below are identified in Table 1.1. Water was heated to 60-70° C. with agitation using a large choppingblade (100 rpm).2. Phase A was added while mixing with large chopping blade for 1 hr(500-900 rpm) until pigments dispersed (approx. 1 hr).3. Phase B was added and the mixture was stirred with chopping blade(900 rpm) until a smooth texture was achieved. The temperature was thenincreased to 70-90° C.4. Phase C was melted in a water bath at 60-90° C. and added slowly tothe mixture in step 3. After phase C was added the resulting mixture wasemulsified at 1200-1500 rpm for 20 min at 60-90° C.5. The mixture was then cooled to less than 50° C., and a solution ofPhase D was added and the composition mixed for 20 min (1200 rpm).6. Once the mixture was homogeneous it was cooled to 60-80° C. andpoured

TABLE 1 Inventive Examples 1-3 Ex. 1 Ex. 2 Ex. 3 Phase Function INCIName Amount (%) A Solvent (d) water QS 43.5 41.7 54.7 Pigment (e) ironoxides 20 20 20 B Emollient butylene glycol 3.9 3.9 3.9 Preservativephenoxyethanol 0.5 0.5 0.5 Preservative sodium sehydroacetate 0.2 0.20.2 sodium hyaluronate 0.2 0.2 0.2 Preservative disodium EDTA 0.2 0.20.2 Preservative caprylyl glycol 0.3 0.3 0.3 Non-associative ammonium1.0 1.0 1.0 (synthetic) polyacryloyldimethyl (a) (I) taurate Associativeammonium 0.5 0.5 0.5 Thickener acryloyldimethyl (synthetic)aaurate/steareth-8 (a) (II) methacrylate copolymer C Emulsifier (b)behenyl alcohol 1.75 1.75 1.75 (CERALUTION ® glyceryl stearate 1.75 1.751.75 H) disodium ethylene 0.75 0.75 0.75 dicocamide-PEG-15 disulfate((b)) glyceryl stearate 0.75 0.75 0.75 citrate D Fillerstyrene/acrylates 3.2 5.0 0.5 copolymer Liquid Fatty PEG-10 dimethicone1.5 1.5 0.4 Substance (c) Liquid Fatty dimethicone (and) 2.0 2.0 0.52Substance (c) dimethicone/ PEG-10/15 crosspolymer Liquid Fatty phenyltrimethicone 3.0 3.0 0.78 Substance (c) Liquid Fatty dimethicone (and)5.0 5.0 1.3 Substance (c) dimethiconol E Wax (f) microcrystalline wax2.5 Wax (f) ozokerite 2.5 Wax (f) beeswax 5 5.0 Wax (f) ceresin 10 Wax(g) polyethylene 5 Viscosity 37.5 40 27.5 (Rheomat, Pa · s Pa · s Pa · sMethod B)¹ ¹Approximate viscosities determined using Method B.

Rheology:

The rheology of the compositions of the invention was compared with thatof two commercially-available anhydrous comparator eye linercompositions. The comparator compositions were as follows:Comparator A: Commercial anhydrous gel eyeliner containing approximately20% more pigments than the inventive compositions. Key ingredients are:Trimethylsiloxysilicate, Cyclopentasiloxane, Isododecane,Cyclohexasiloxane, Ceresin, Caprylyl Methicone, Silica Silylate,Disteardimonium Hectorite, Trieth-Oxycaprylylsilane, Talc, SyntheticFluorphlogopite, Propylene Carbonate, BHT and Tin Oxide.Comparator B: Commercial anhydrous gel eyeliner known for having acreamy texture. Key ingredients are: Isododecane, cyclopentasiloxane,polyethylene, Barium sulfate, trimethylsiloxysilicate, disteardimoniumhectorite, propylene carbonate, lecithin, phenyl trimethicone,ethylhexylglycerin, hydrogenated polyisobutene and methicone.The rheology of the compositions was measured as follows: Data wascollected on a TA Instrument AR G2 Rheometer. All values were measuredwith a 20 mm 2° cone (990901) in continuous mode unless otherwise stated(Method A).

Parameters:

Test type: Continuous modeRamp: shear rate 1/s, from 0.01-1000 1/sDuration: 10 minutes

Mode: log

Sample: points per decade=5

Temperature: 25° C.

Values:

Viscosities (Pa*s) were reported at the onset of the run at a low shearrate (0.015 s⁻¹) and at the end of the run at a high shear rate (990s⁻¹).The results of the rheological comparisons are summarized below in Table2.

TABLE 2 Viscosity¹ Viscosity¹ (Pa*s @ 0.015 1/s) (Pa*s@ 990 1/s)Composition (low shear) (high shear) Slope² Comparator A 49330 0.36 −1.0Comparator B 3829 0.19 −0.86 Composition 26300 1.79 −0.85 of Example 1Composition 39090 2.46 −0.83 of Example 2 Composition 16450 1.09 −0.81of Example 3 ¹Using method A ²Slope refers to the slope of a viscosity(Pa · s) versus shear rate (1/s) graph

The steady shear flow of the inventive water-based gel eyelinercompositions with waxes in absence of film formers were compared toanhydrous Competitors A and B. The inventive compositions comprising theindicated components in particular ratios provided varying shearthinning profiles. The rheological profile was optimized to provideoptimal control of pickup (low shear viscosity) and application (highshear viscosity) of the compositions. As is shown in Table 2, the “lowshear” viscosities of the inventive compositions with a ratio ofa(i)/a(ii) of 2:1 (Examples1-3) can be increased by the addition ofdifferent ratios of waxes providing yield solvent-free, water-based gelshaving “low shear” viscosities ranging from 10000-40000 Pa*s, which iscomparable to Competitor A that similarly contains waxes, yet does notcontain water. The highest ratio exemplified was obtained using Ceresin(Example 2).

High shear viscosities on a rheological graph represent the applicationregion of a product (such as the application of a cosmetic on skin). Asshown with Examples 1-3, the inventive compositions exemplified have“high shear” viscosities ranging from about 1 to about 3 Pa*s. This canbe further attenuated to lower viscosities using alternate ratios ofa(i)/a(ii). Examples with “high shear” viscosities closest to CompetitorA have comparable or better application properties.

The slope of the viscosity (Pa*s) versus shear rate (1/s) graph gives anindication of shear thinning properties, which also impacts application.The slope of the viscosity (Pa*s) versus shear rate (1/s) graph foranhydrous wax containing formulas of Competitor A and B are from about−0.86 to about −1.0. Inventive Examples 1-3 all have comparable shearthinning properties (close slopes) to anhydrous Competitors A and B, butachieve this in an aqueous emulsion system. It is noteworthy that thisis achieved without the use of film formers.

What is claimed is:
 1. A water-based gel cosmetic compositioncomprising: (a) a viscosity increasing system comprising (I) at leastone synthetic non-associative thickening polymer; and (II) at least onesynthetic associative thickening polymer; (b) at least one emulsifier;(c) at least one liquid fatty substance; (d) water; (e) optionally apigment; and (f) optionally at least one wax; wherein the compositionhas a viscosity of from about 2,000 Pa·s to about 90,000 Pa·s at lowshear rate.
 2. The composition of claim 1 wherein the ratio of the atleast one synthetic non-associative thickening polymer (a)(I) to the atleast one synthetic associative thickening polymer (a)(II) is greaterthan 1:1.
 3. The composition of claim 2 wherein the viscosity increasingsystem is present in an amount of from about 0.11% to about 4%, byweight, relative to the total weight of the composition.
 4. Thecomposition of claim 3 wherein the viscosity increasing system (a)comprises (I) from about 0.01% to about 2.0% by weight of at least onesynthetic non-associative thickening polymer; and (II) from about 0.1%to about 2.0% by weight of at least one synthetic associative thickeningpolymer, by weight, relative to the total weight of the composition. 5.The composition of claim 4 wherein the at least one emulsifier (b) ispresent in an amount of from about 0.1% to about 7.5%, by weight,relative to the total weight of the composition.
 6. The composition ofclaim 5 wherein the at least one liquid fatty substance (c) is presentin an amount of from about 0.1% to about 30%, by weight, relative to thetotal weight of the composition.
 7. The composition of claim 6 whereinthe water (d) is present in an amount of from about 5% to about 60%, byweight, relative to the total weight of the composition.
 8. Thecomposition of claim 7 wherein the ratio of the at least one syntheticnon-associative thickening polymer (a)(I) to the at least one syntheticassociative thickening polymer (a)(II) is from about 1.5:1 to about 3:1.9. The composition of claim 8 wherein the at least one emulsifier (b) isselected from fatty alcohols, fatty esters of polyols, fatty acids, andmixtures thereof.
 10. The composition of claim 9 wherein the emulsifier(b) is a gemini surfactant.
 11. The composition of claim 10 wherein theat least one synthetic non-associative thickening polymer (a)(I) ispresent in an amount of about 1% by weight, the at least one syntheticassociative thickening polymer (a)(II) is present in an amount of about0.5% by weight, the at least one emulsifier (b) is present in an amountof about 0.75% by weight, the at least one liquid fatty substance (c) ispresent in an amount of from about 3% to about 11.5% by weight, andwater (d) is present in an amount of from about 40% to about 55% byweight, relative to the weight of the final composition.
 12. Thecomposition of claim 11 comprising wax.
 13. A water-based gel cosmeticcomposition comprising: (a) a viscosity increasing system comprising (I)at least one synthetic non-associative thickening polymer; and (II) atleast one synthetic associative thickening polymer; (b) at least oneemulsifier; (c) at least one liquid fatty substance; (d) water; (e)optionally a pigment; and (f) optionally at least one wax; wherein theratio of the at least one synthetic non-associative thickening polymer(a)(I) to the at least one synthetic associative thickening polymer(a)(II) is less than or equal to 1:1; all percentages and ratios beingbased on the total weight of the composition.
 14. The composition ofclaim 13 wherein the viscosity increasing system (a) is present in anamount of from about 0.11% to about 4%, by weight, relative to the totalweight of the composition.
 15. The composition of claim 14 wherein theat least one synthetic non-associative thickening polymer (a)(I) ispresent in an amount of from about 0.0% to about 2.0%, by weight,relative to the total weight of the composition.
 16. The composition ofclaim 15 wherein the at least one synthetic associative thickeningpolymer (a)(II) is present in an amount of from about 0.01% to about2.0%, by weight, relative to the total weight of the composition. 17.The composition of claim 16 wherein the at least one emulsifier (b) ispresent in an amount of from about 0.4% to about 7.5%, by weight,relative to the total weight of the composition.
 18. The composition ofclaim 17 wherein the at least one liquid fatty substance (c) is presentin an amount of from about 0.1% to about 30%, by weight, relative to thetotal weight of the composition.
 19. The composition of claim 18 whereinthe water (d) is present in an amount of from about 5% to about 60%, byweight, relative to the total weight of the composition.
 20. Thecomposition of claim 19 wherein ratio of the at least one syntheticnon-associative thickening polymer (a)(I) to the at least one syntheticassociative thickening polymer (a)(II) is from about 0:0.5 to about 1:3.21. The composition of claim 20 having a viscosity of from about 3,000Pa·s to about 90,000 Pa·s at low shear rate.
 22. The composition ofclaim 21 wherein the at least one emulsifier (b) is selected from fattyalcohols, fatty esters of polyols, fatty acids, and mixtures thereof.23. The composition of claim 22 wherein the at least one syntheticnon-associative thickening polymer (a)(I) is present in an amount offrom about 0% to about 1.5% by weight, the at least one syntheticassociative thickening polymer (a)(II) is present in an amount of fromabout 1.0% to about 1.5% by weight, the at least one emulsifier (b) ispresent in an amount of about 0.75% by weight, the at least one liquidfatty substance (c) is present in an amount of from about 3% to about11.5% by weight, and water (d) is present in an amount of from about 46%to about 48% by weight, relative to the weight of the final composition.24. The composition of claim 13 wherein the synthetic non-associativepolymer (a)(I) is present in an amount of 0%, by weight, relative to thetotal weight of the composition.
 25. The composition of claim 24comprising wax.
 26. A kit for making up the eyes comprising a pen-typeapplicator containing the composition of claim
 1. 27. A method of makingup or enhancing the appearance of the eye by applying to the eyelids,topically, a composition according to claim 1.